CN103589538A - Cleaning liquid of solar silicon wafer as well as using method thereof - Google Patents
Cleaning liquid of solar silicon wafer as well as using method thereof Download PDFInfo
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- CN103589538A CN103589538A CN201310384324.5A CN201310384324A CN103589538A CN 103589538 A CN103589538 A CN 103589538A CN 201310384324 A CN201310384324 A CN 201310384324A CN 103589538 A CN103589538 A CN 103589538A
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- scavenging solution
- silicon chip
- ultrasonic cleaning
- pure water
- solar silicon
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Abstract
The invention discloses a cleaning liquid of a solar silicon wafer as well as a using method thereof. The cleaning liquid consists of the following components in percentage by weight: 20-30% of citric acid, 0.1-1% of hydrofluoric acid, 5-20% of hydrogen peroxide, 1-2% of a pH adjustor, 10-25% of a surfactant, 2-5 parts of a dispersing agent and the balance of pure water. The cleaning liquid disclosed by the invention has the advantages of improved cleaning efficiency, excellent cleaning effect and the like, is more convenient to apply and easy to operate and control, and meanwhile can effectively reduce the environmental pollution. Meanwhile, by using the cleaning liquid disclosed by the invention, the texturing unevenness rate can be extremely reduced.
Description
Technical field
The present invention relates to manufacture of solar cells technical field, particularly a kind of scavenging solution of solar silicon wafers and using method thereof.
Background technology
Along with the exhaustion day by day of conventional energy resources, sun power easy to clean more and more receives people's concern.In solar cell fabrication process, silicon chip is as the core component of solar cell, and its various performance parameters directly affects the generating efficiency of solar cell.
In general, the silicon chip for the preparation of solar cell is to be formed by silicon rod cutting.In industry, conventionally use at present line cutting technology, the metal cutting line of high-speed motion cuts into by silicon rod the silicon chip that thickness is 200 microns of left and right under auxiliary liquid, tackiness agent auxiliary.Generally, can there are various pollutents in silicon chip surface, these pollutents generally derive from metallic particles, the silicon grain of line of cut and silicon chip wearing and tearing generation, the auxiliary using in cutting process, adhesive residue, and the various pollutent precipitations in handling process etc.At silicon chip, store, in the process of transportation, because pollutent remains in the overlong time of silicon chip surface, pollutent is oxidized, oxidize contaminants strong adsorption, at silicon chip surface, cannot clean up by current cleaning way.The existence of these pollutents will affect the complete processing in later stage, while making making herbs into wool, residual compound, metal pollutant and the soda acid of silicon chip surface is residual too much makes silicon chip surface occur hickie, produces aberration phenomenon, the efficiency of conversion that reduces solar cell, affects yield rate and quality product.Therefore, silicon wafer cleaning process is most important in solar cell preparation technology.
Existing cleaning silicon chip is used the method for chemical corrosion conventionally, conventionally adopts highly basic (such as KOH, NaOH etc.) solution or HNO
3reach with the hybrid corrosion silicon chip of HF the object of removing silicon chip precipitated impurities.Yet strong base solution easily causes the poor effect of polishing, even and if diluent, speed of reaction is still very fast, and depth of corrosion is difficult to control.For another fruit, adopt HNO
3with the method clean contaminants of the hybrid corrosion silicon chip of HF, HNO
3can produce poisonous oxides of nitrogen gas with the mixed solution of HF, increase the weight of the pollution in solar battery sheet production and the stopping property of equipment is proposed to high requirement, improved production cost, and there is the process of a reacting activation and autocatalysis in the corrosion of this scavenging solution, speed of response is first slow rear fast, wayward.
The disclosure of the invention of CN 102477358 A a kind of silicon slice detergent, contain tensio-active agent, solubility promoter, metal complex, suspension agent, silicon slice corrosion agent and water, described tensio-active agent contains water-soluble fluorine-containing nonionogenic tenside and alcohol ether surfactants, and the weight ratio of described water-soluble fluorine-containing nonionogenic tenside and alcohol ether surfactants is 1: 10 to 1: 40.Described silicon slice corrosion agent is selected from following one or more: sodium hydroxide, potassium hydroxide and sodium carbonate.This silicon slice detergent is alkaline cleaner, exists speed of reaction still very fast, the unmanageable defect of depth of corrosion.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect that prior art exists, a kind of scavenging solution of solar silicon wafers is provided, there is raising cleaning efficiency, the advantages such as cleaning performance is good, use this scavenging solution easy to clean, easy handling is controlled, and can effectively reduce environmental pollution simultaneously.Meanwhile, the scavenging solution of the application of the invention, can reduce making herbs into wool flower sheet rate greatly.
The present invention also provides the using method of the scavenging solution of above-mentioned solar silicon wafers, easy and simple to handle.
The technical solution adopted for the present invention to solve the technical problems is:
A scavenging solution for solar silicon wafers, described scavenging solution is mixed and is formed by the component of following mass percent meter: citric acid 20-30%, hydrofluoric acid 0.1-1%, hydrogen peroxide 5%-20%, pH adjusting agent 1%-2%, tensio-active agent 10-25%, dispersion agent 2-5%, all the other are pure water.
As preferably, described tensio-active agent is triethanolamine oleate or isomery polyoxyethylenated alcohol.Tensio-active agent combination is used rear effect can decline on the contrary.
As preferably, described dispersion agent is selected from one or more in sodium-metaphosphate, trisodium phosphate, tripoly phosphate sodium STPP.
As preferably, described pH adjusting agent is selected from one or more in lactic acid, acetic acid, Tripotassium Citrate.
The present invention adopts acidic cleaner, and main component is citric acid, and citric acid is pollution-free for nitric acid, corrodibility to equipment is lower, and by coordinating of citric acid and hydrofluoric acid, can effectively remove the oxide compound of silicon chip surface, can reduce greatly making herbs into wool flower sheet rate.
The adsorptive power that adds tensio-active agent to remove silicon chip surface particle and silicon chip reaches the object of cleaning silicon chip.In scavenging solution of the present invention, add dispersion agent remove slicing processes in residual oil.By control the corrosion of scavenging solution to silicon chip with hydrogen peroxide.By using by pH adjusting agent, regulate pH value simultaneously, make it control pH between 2-5, the one, for Stabilizing Hydrogen Peroxide, avoid a large amount of decomposition of hydrogen peroxide in reaction, cause hydrogen peroxide concentration to decline, solved and in cleaning, obtained the problem of constantly adding hydrogen peroxide; The 2nd, in order to control speed of response, guarantee the In Apparent Good Order and Condition of silicon chip after plating silicon nitride anti-reflecting film.
The using method of scavenging solution, comprise the steps:
(1) silicon chip being cut into by silicon rod is put into pure water and carry out ultrasonic cleaning 5-10 minute;
(2) by the silicon chip after step (1) ultrasonic cleaning, put into scavenging solution ultrasonic cleaning 10-30 minute;
(3) silicon chip after step (2) ultrasonic cleaning is cleaned up with pure water.
Aforesaid method is simple to operate, is easy to control, and cleaning performance is good.
As preferably, temperature when step (2) scavenging solution cleans is controlled at 20-40 ℃.At this temperature, the cleaning performance of scavenging solution performance is best.
The invention has the beneficial effects as follows:
1, there is raising cleaning efficiency, the advantage such as cleaning performance is good.
2, use scavenging solution easy to clean of the present invention, easy handling is controlled, and can effectively reduce environmental pollution simultaneously.
3, the scavenging solution of the application of the invention, can reduce making herbs into wool flower sheet rate greatly.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopting and equipment etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.
Embodiment 1:
Formula:
Scavenging solution is mixed and is formed by the component of following mass percent meter: citric acid 20%, and hydrofluoric acid 0.5%, hydrogen peroxide 5%(is commercially available, industrial hydrogen peroxide, mass concentration 30%), acetic acid 1%, triethanolamine oleate 20%(is commercially available), sodium-metaphosphate 5%, all the other are pure water.
Using method:
(1) silicon chip being cut into by silicon rod is put into pure water and carried out ultrasonic cleaning 5 minutes;
(2) by the silicon chip after step (1) ultrasonic cleaning, put into scavenging solution ultrasonic cleaning 15 minutes, cleaning temperature is 30 ℃;
(3) more than the silicon chip after step (2) ultrasonic cleaning is finally cleaned to two roads with the ultrasonic overflow of pure water, per pass 5 minutes.
Embodiment 2:
Formula:
Scavenging solution is mixed and is formed by the component of following mass percent meter: citric acid 30%, hydrofluoric acid 0.1%, hydrogen peroxide 10%(is commercially available, industrial hydrogen peroxide, mass concentration 30%), lactic acid 0.5%, acetic acid 0.5%, 10%(is commercially available for isomery polyoxyethylenated alcohol), trisodium phosphate 1%, sodium-metaphosphate 1%, all the other are pure water.
Using method:
(1) silicon chip being cut into by silicon rod is put into pure water and carried out ultrasonic cleaning 10 minutes;
(2) by the silicon chip after step (1) ultrasonic cleaning, put into scavenging solution ultrasonic cleaning 10 minutes, cleaning temperature is 40 ℃;
(3) more than the silicon chip after step (2) ultrasonic cleaning is finally cleaned to two roads with the ultrasonic overflow of pure water, per pass 5 minutes.
Embodiment 3:
Formula:
Scavenging solution is mixed and is formed by the component of following mass percent meter: citric acid 21%, and hydrofluoric acid 1%, hydrogen peroxide 20%(is commercially available, industrial hydrogen peroxide, mass concentration 30%), Tripotassium Citrate 2%, triethanolamine oleate 25%(is commercially available), sodium-metaphosphate 3%, all the other are pure water.
Using method:
(1) silicon chip being cut into by silicon rod is put into pure water and carried out ultrasonic cleaning 5 minutes;
(2) by the silicon chip after step (1) ultrasonic cleaning, put into scavenging solution ultrasonic cleaning 30 minutes, cleaning temperature is 20 ℃;
(3) more than the silicon chip after step (2) ultrasonic cleaning is finally cleaned to two roads with the ultrasonic overflow of pure water, per pass 5 minutes.
Comparative example 1
This routine difference from Example 1 is, does not add triethanolamine oleate in scavenging solution formula.
Comparative example 2
This routine difference from Example 1 is, does not add sodium-metaphosphate in scavenging solution formula.
Comparative example 3
This routine difference from Example 1 is, in scavenging solution formula, the usage ratio of triethanolamine oleate is 30%.
Comparative example 4
This routine difference from Example 1 is, scavenging solution formula:
Scavenging solution is mixed and is formed by the component of following mass percent meter: nitric acid 30%, and hydrofluoric acid 1%, hydrogen peroxide 20%(is commercially available, industrial hydrogen peroxide, mass concentration 30%), all the other are pure water.
Comparative example 5
Do not use scavenging solution to clean, only pass through repeatedly ultrasonic cleaning silicon chip in pure water.
Aforesaid method cleaning silicon chip each after 10,000, its cleaning performance is as following table:
| Group | Making herbs into wool flower sheet rate | Electromagnetic plate average efficiency |
| Embodiment 1 | 0.21% | 18.29% |
| Embodiment 2 | 0.23% | 18.27% |
| Embodiment 3 | 0.22% | 18.28% |
| Comparative example 1 | 0.34% | 18.25% |
| Comparative example 2 | 0.58% | 18.28% |
| Comparative example 3 | 0.27% | 18.33% |
| Comparative example 4 | 0.37% | 18.30% |
| Comparative example 5 | 1.07% | 18.19% |
Scavenging solution of the present invention is with the conventional HNO using
3/ HF scavenging solution (comparative example 4) and do not use scavenging solution to contrast, can obviously find out from upper table, the scavenging solution of the application of the invention has improved the qualification rate of making herbs into wool operation to a great extent, and the efficiency of electromagnetic plate does not also reduce simultaneously.In a word, silicon chip of solar cell scavenging solution of the present invention, formula is simple, and cleaning performance is good, can effectively remove the contamination of silicon chip surface, improves making herbs into wool quality and good article rate, and this contaminated cleaning solution is few simultaneously, is easy to process, and reduces to a certain extent production cost.
Above-described embodiment is a kind of preferably scheme of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Claims (6)
1. a scavenging solution for solar silicon wafers, is characterized in that: described scavenging solution is mixed and formed by the component of following mass percent meter: citric acid 20-30%, hydrofluoric acid 0.1-1%, hydrogen peroxide 5%-20%, pH adjusting agent 1%-2%, tensio-active agent 10-25%, dispersion agent 2-5%, all the other are pure water.
2. the scavenging solution of a kind of solar silicon wafers according to claim 1, is characterized in that: described tensio-active agent is triethanolamine oleate or isomery polyoxyethylenated alcohol.
3. the scavenging solution of a kind of solar silicon wafers according to claim 1 and 2, is characterized in that: described dispersion agent is selected from one or more in sodium-metaphosphate, trisodium phosphate, tripoly phosphate sodium STPP.
4. the scavenging solution of a kind of solar silicon wafers according to claim 1 and 2, is characterized in that: described pH adjusting agent is selected from one or more in lactic acid, acetic acid, Tripotassium Citrate.
5. the using method of the scavenging solution of solar silicon wafers as claimed in claim 1, is characterized in that: comprise the steps:
(1) silicon chip being cut into by silicon rod is put into pure water and carry out ultrasonic cleaning 5-10 minute;
(2) by the silicon chip after step (1) ultrasonic cleaning, put into scavenging solution ultrasonic cleaning 10-30 minute;
(3) silicon chip after step (2) ultrasonic cleaning is cleaned up with pure water.
6. using method according to claim 5, is characterized in that: temperature when step (2) scavenging solution cleans is controlled at 20-40 ℃.
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| CN201310384324.5A CN103589538B (en) | 2013-08-30 | 2013-08-30 | Cleaning liquid of solar silicon wafer as well as using method thereof |
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| CN103589538A true CN103589538A (en) | 2014-02-19 |
| CN103589538B CN103589538B (en) | 2015-04-29 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404628A (en) * | 2014-11-14 | 2015-03-11 | 大连理工大学 | Surfactant mixture for polysilicon suede making, suede making solution containing the same and suede making method |
| CN104893848A (en) * | 2015-06-09 | 2015-09-09 | 武汉宜田科技发展有限公司 | Degradable environment-friendly silicon slice detergent and preparation method thereof |
| CN106098810A (en) * | 2016-06-27 | 2016-11-09 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of crystal silicon solar energy battery suede structure |
| CN106591009A (en) * | 2016-12-27 | 2017-04-26 | 常州协鑫光伏科技有限公司 | Cleaning agent for silicon slice alkali cleaning |
| CN108172500A (en) * | 2017-12-15 | 2018-06-15 | 上海申和热磁电子有限公司 | A kind of method using the removal polished silicon slice surface contamination of room temperature HF acid |
| CN108559639A (en) * | 2018-01-09 | 2018-09-21 | 江苏荣马新能源有限公司 | A kind of cleaning solution for the surface treatment of black silicon cell |
| CN108831966A (en) * | 2018-07-06 | 2018-11-16 | 安徽腾奎智能科技有限公司 | A kind of cleaning solution for photovoltaic cell board group |
| CN109868193A (en) * | 2017-12-05 | 2019-06-11 | 南风化工集团股份有限公司 | A kind of solar panels cleaning agent |
| CN111154565A (en) * | 2019-12-31 | 2020-05-15 | 宁夏中晶半导体材料有限公司 | Silicon material cleaning agent |
| CN112126534A (en) * | 2020-09-01 | 2020-12-25 | 武汉宜田科技发展有限公司 | Neutral degumming agent for diamond wire cutting single/polycrystalline silicon rod |
| CN112547663A (en) * | 2020-11-24 | 2021-03-26 | 昆山硅瑞自动化设备有限公司 | Silicon edge leather cleaning process |
| CN112940875A (en) * | 2021-02-05 | 2021-06-11 | 嘉兴市小辰光伏科技有限公司 | Solar cell silicon wafer cleaning agent and solar cell silicon wafer cleaning method |
| CN115197791A (en) * | 2022-08-08 | 2022-10-18 | 苏州协鑫光伏科技有限公司 | Surfactant for pre-cleaning silicon wafer, and preparation method and application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404628B (en) * | 2014-11-14 | 2017-01-04 | 大连理工大学 | One class is for the surfactant blend of polysilicon making herbs into wool, the Woolen-making liquid containing this compound and etching method |
| CN104404628A (en) * | 2014-11-14 | 2015-03-11 | 大连理工大学 | Surfactant mixture for polysilicon suede making, suede making solution containing the same and suede making method |
| CN104893848A (en) * | 2015-06-09 | 2015-09-09 | 武汉宜田科技发展有限公司 | Degradable environment-friendly silicon slice detergent and preparation method thereof |
| CN104893848B (en) * | 2015-06-09 | 2018-04-03 | 武汉宜田科技发展有限公司 | A kind of degradable environment friendly silicon chip detergent and preparation method thereof |
| CN106098810B (en) * | 2016-06-27 | 2018-11-13 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of crystal silicon solar energy battery suede structure |
| CN106098810A (en) * | 2016-06-27 | 2016-11-09 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of crystal silicon solar energy battery suede structure |
| CN106591009A (en) * | 2016-12-27 | 2017-04-26 | 常州协鑫光伏科技有限公司 | Cleaning agent for silicon slice alkali cleaning |
| CN109868193A (en) * | 2017-12-05 | 2019-06-11 | 南风化工集团股份有限公司 | A kind of solar panels cleaning agent |
| CN108172500A (en) * | 2017-12-15 | 2018-06-15 | 上海申和热磁电子有限公司 | A kind of method using the removal polished silicon slice surface contamination of room temperature HF acid |
| CN108559639A (en) * | 2018-01-09 | 2018-09-21 | 江苏荣马新能源有限公司 | A kind of cleaning solution for the surface treatment of black silicon cell |
| CN108831966A (en) * | 2018-07-06 | 2018-11-16 | 安徽腾奎智能科技有限公司 | A kind of cleaning solution for photovoltaic cell board group |
| CN111154565A (en) * | 2019-12-31 | 2020-05-15 | 宁夏中晶半导体材料有限公司 | Silicon material cleaning agent |
| CN112126534A (en) * | 2020-09-01 | 2020-12-25 | 武汉宜田科技发展有限公司 | Neutral degumming agent for diamond wire cutting single/polycrystalline silicon rod |
| CN112547663A (en) * | 2020-11-24 | 2021-03-26 | 昆山硅瑞自动化设备有限公司 | Silicon edge leather cleaning process |
| CN112940875A (en) * | 2021-02-05 | 2021-06-11 | 嘉兴市小辰光伏科技有限公司 | Solar cell silicon wafer cleaning agent and solar cell silicon wafer cleaning method |
| CN115197791A (en) * | 2022-08-08 | 2022-10-18 | 苏州协鑫光伏科技有限公司 | Surfactant for pre-cleaning silicon wafer, and preparation method and application thereof |
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